Patent GB-798635-A (GB)
Title: Lubricating oil compositions
IPC: C07F9/40
Filed: 1956-06-18
Abstract: Partial or full salts of branched chain primary or secondary aliphatic or cycloaliphatic amines having at least 8 carbon atoms and organic phosphorus acids of general formula: <FORM:0798635/IV (b)/1> where R is a hydrocarbon or halohydrocarbon radical, X is a non-metallic element of Group VIb of the Periodic Table, and y is H, XH, or R are referred to for use as lubricant additives (see Group III).  C8-36 amines are preferred, extensive lists being given including 1,1,3,3-tetramethyl butyl amine, isoheptyl diethyl carbinylamine, di-(2-ethyl hexyl) amine, dibromo-dioctadecylamine, butyl ricinoleylamine, dicyclopentylamine, benzyl 2-ethyl hexyl amine, allyl octyl amine, N-n-dodecyl diethylene triamine, N-2-ethyl hexyl N-hexadecyl triethylene tetramine, and N,N1-diallyl trimethylene diamine.  Many examples are given of paraffinic and alicyclic hydrocarbon-, chlorohydrocarbon-, bromohydrocarbon-, and chlorobromohydrocarbon - substituted phosphinic, thiophosphinic, phosphonic, thiophosphonic, and selenophosphonic acids which may be used to form the amine salts.  The salts have the general formul : <FORM:0798635/IV (b)/2> where A is the amine and R1 is R or H.  They may be prepared by reacting the selected amine and acid in a solvent or in the presence of water under suitable conditions such as mixing at room temperature, stirring or heating.  They may be purified by recrystallization.  A long list of preferred salts includes salts of trifluoromethane phosphonic acid and trichloromethane dithiophosphonic acid.  The preparation is described of compounds of the formula: <FORM:0798635/IV (b)/3> by the reaction at 50 DEG  C. of 1 mol. of trichloromethane phosphonic acid and 2 mols. of A3, 1 mol. of A3 and 2 mols. of A1 respectively.  A3 is a mixture of t-alkyl (C18-24) primary amines and A1 a mixture of t-alkyl (C12-15) primary amines.  In examples the above amines are incorporated in lubricating oil compositions, the amine and acid being added to the oil separately.  Specifications 505,016, [Group IV], 634,720, 637,389 and 689,872 are referred to.ALSO:A lubricating oil composition comprises a major proportion of a lubricating oil and minor proportions of (a) salt of a branched-chain primary or secondary aliphatic or cycloaliphatic amine having at least 8 carbon atoms and an organic phosphorus acid of the general formula <FORM:0798635/III/1> where R is a hydrocarbon or halohydrocarbon radical, X is a non-metallic element of Group VI (b) of the Periodic Table and Y is H, XH, or R; and (b) a partial ester of a polyhydric alcohol and an organic carboxylic or sulphonic acid.  The lubricating oil is preferably a mineral or sulphurized mineral oil but synthetic oils may also be used, e.g. polymerized olefins, alkylated aromatics, polyalkyl silicone polymers, hydrogen sulphide adducts of unsaturated ethers and thioethers and esters such as di-(2-ethyl hexyl) sebacate.  The amine used in component (a) preferably contains from 8 to 36 carbon atoms, extensive lists of branchedchain primary and secondary amines being given, including dibromodioctadecyl amine and diricinoleyl amine.  Many examples are given of hydrocarbon, chloro-hydrocarbon and bromohydrocarbon substituted phosphinic, thiophosphinic, phosphonic, thio-phosphonic and seleno-phosphonic acids which may be used to form the amine salts which have the general formul <FORM:0798635/III/2> where A is the amine and R1 is R or H.  A solubilizing agent may be associated with the amine salt, examples being oil-soluble aliphatic alcohols and/or thiols which may be straight or branched chain, saturated or unsaturated, and which contain at least 6 carbon atoms and the fatty alcohols and their thiol analogues. The polyhydric alcohols used to form the esters of (b) may be water-soluble alkane polyols of from 2 to 6 carbon atoms, e.g. propylene glycol and mannitol; ether alcohols, e.g. triethylene glycol and hexitans such as mannitans which may be etherified with alkylene oxides or glycols; or sugars.  The acids used to form the esters include saturated or unsaturated aliphatic mono- or polycarboxylic acids, cycloaliphatic carboxylic acids, aromatic carboxylic acids, aromatic sulphonic acids and higher alkane sulphonic acids.  Optional ingredients mentioned are fatty acids of at least 12 carbon atoms, esters of these acids and waxes, and derivatives obtained from them by sulphurization, halogenation and/or polymerization, e.g. sulphurized and sulphochlorinated fats and fatty oils; anti-oxidants, e.g. alkyl phenols; corrosion inhibitors, e.g. mercaptobenzothiazole, nitrites, and 9 to 11 carbon fatty acids; and anti-form agents, e.g. silicone polymers, organic phosphates and aliphatic alcohols.  A composition typical of several examples comprises: sulphurized oleic acid, glycerol mono-oleate, trichloromethane phosphonic acid, a commercial mixture of 12-15 carbon branchedchain primary amines and SAE 90 mineral oil. Specifications 505,016 [Group IV], 634,720, 637,389 and 689,872, [Group IV (b)], are referred to.